Production of metal hydrides



June 4, 1946., P. P. ALEXANDER PRODUCTION OF METAL HYDRIDES Filed Sept. 30, l944 VAUUM INVENTOR PETER R ALEXANDER ATTORNEY5 e favor.

' Calcium hydride for the purpose of generating Patented June 4, 1946 &401523 PRODUCTION OF METAL HYDBIDES Peter P. Alexander; Marblehead, Masa., asignor to Metal Hydrlde Icorporated, Beverly, Mase.. corporation of Massaelusetts i Application September 30, 1944, Serial No. 556.577

This invention relates to metal hydrides and has for its object certain improvements in the method oi' producing ''etal-hydrides.- 'The product of the invention is particularly useful in the production 'of hydrogen gas in the field, for inflating balloons and the like. Among several available methods tor generating hydrogen is the action of calcium hydride on water. since this reaction takes place at room temperature, the generation of hydrogen can be carried out simply by introducing the calcium hydrideinto a suitable container filled with water. This process finds little or no use, however, because of the high cost of the calcium used to produce the calciun hydride. Another method for generating hydrogen is to react ferro-silicon with caustic soda. The reaction is ot a complex nature, subject to temperature variations so that the rate of generation of hydrogen varies considerably under diflerent conditions. The caustic soda is dangerous to handle, on account of injury to body and clothing, and the process finds little hydrogen gas has also been made by heating calcium oxide and magnesium in the presence oi' hydrogen, !or example, as described in my U. S. Patent 2982434. If the charge oi' calcium oxide 2 dled than magnesium, it has been proposed to produce calcium hydride by reacting calcium oxide and aluminum in the presence of hydrogen gas. Magnesium'has appreciable vapor pressure at the temperature of formation of the calcium hydride. Aluminum, on the contrary, does not sublime nor evaporate until heated to a temperature of about 1200 C. Calcium hydride cannot form at this temperature, since it dissociates at lower temperatures. i Aluminum will not react with calcium'oxide below the melting point of the aluminum; and, after it is melted, the aluninum forms isolated globules covered with a layer oi' aluminum oxide which prevent: contact oi aluminum metal with the calcium' oxide.

While alu'ninum has been used to reduce calciunroxide, it has been done in' a way that is not applicable to the production oi' calcium hy- `dride. For example, pieces of calcium oxide are sunk in a bath of molten aluminum so that calcium is released to form an alloy with the aluminum. It has also been proposed to heat a charge and magnesiun is raised in temperature, a point is reached, below that at which the magnesiumo! hydrogen when the temperature of the charge.

approaches the melting point of magnesim. which is indicated by a large increase in hydrogen pressure. 'Il' the temperature is raised to the melting point of the magnesium too rapidly, the rise in hvdrogen pressure is substantialy explosive in character and' there'i'ore dangerous. Magnesium is highly reactive and must be handled with considerable care; This is particularly true when the magnesium is mechanically subdivided to produce smaller particles !or use in the charge.

since aluminum is cheapethan magnesium of aluminum i'oil and calcium odde under vacuum to a temperature at which the aluminum melts and then place the charge under pressure to force the molten aluminum into the evacuated pores ot calcium oxide to en'ect reduction and volatilization of .the calcium. These procedures are; obviously, not adapixad for the production of aluminum oxide, which prevents contact of the aluminum itself with the' calcium oxide. The coating of refractory aluminum oxide prevents or greatly inhibits the chemical reaction between the aluminum and the calciun oxide. since aluminum does not sublime, it remains enveloped in its aluminum oxide coating. I( the heating of the mixture of calcium oxide and iinely divided aluminum is carried out in an atmosphere of hy-.

drogen. especially pure dry hydrogen, little or no reaction will take place. The hydrogen m'a: prevent additionloxidation oi aluminum particles, but it cannot remove the retractory costing oi' aluminum oxide always present-on particles o! aluminum.

' or calcium or ferro-silicon and is saier to hanss To overcome this inherent dliliculty, it has a 3 also been proposed to use molten aluminum by passing it into a retort containing the calcium oxide. the molten aluminum being introduced in the form of a spray. -This does not give satisfactory results. The molten globules of aluminum may initially be entirely free from an outside coating of aluminum oxide and the reaction with calcium oxide may start, but as soon as oxygen is removed from the calcium oxide it neceasarlly produces a coating of aluminum oxide on the molten globules of aluminum and the further reduction of calcium oxide is greatly inhibited or stopped.

To overcome the disadvantageous eflects of the refractory coating of aluminum oxide on the aluminum ;zartlcles or globules of molten aluminum. it has lil! &wise been proposcd to agitate the charge by rolling or tumbling. This procedure does not give satisfactory results, since the small molten globules of aluminum encased in the adherent and continuous layer or coating of aluminum oxide are merely rolled in the mass of calcium oxide particles somewhat as drops of water in dust. The molten metaliic aluminum itself does not come in contact with the calcium oxide particles to any substantial extent.

Aa a result of my investigations I have discovered that if the process is properly conducted, metal hydrides may be produced nevertheless by reacting a hydride-i'orming metal compound with aluminum in a reaction zone to reduce the metal compound, distilling the reduced metal, condensing the distilled metal in a cooler part of the reaction zone, and then admitting hydrogen gas to the reaction zone to convert the condensed metal to the desired metal hydride, the dimculties enumerated may,-for the most part, be overcome. I have found that the process is especially adapted to the production of the hydrides of the alkaline-earth metale, such as calcium, strontium and barium. To achieve the' desired result, I have found that it is necessary to efl'ect the removal orupture of the refractory coating of aluminum oxide, at least in part, from the particles or globules of aiuminum; 'and that this may be done in several ways, so that molten unoxidized metallic aluminum is brought into reactive contact with the' hydride-forming metal compound.

In accordance with one of the methods a charge of the hydride-forming metal compound, for example calcium oxide. and aiuminum particles are heated in a closed retort. As the temperature of the charge is eievated, a vacuum is estabiished in the retort to remove air and moisture. The chare is placed under sumcient vacuum as reduction proceeds to cause expansion of the molten aluminum globules within the refractory envelope of aluminum oxide and, due to the appreciable vapor pressure of the aluminum at that temperature. the unoxidired aluminum is brought into contact with the surrounding particles of calcium oxide, thua bringing the calcium oxide and unoxidied luminum into reactive contact with one another. The reduced metal is distilled and condensed in a cooler part oi' the retort. Hydrogen both, with thecharge of hydride-forming metal compound and aluminum in a retort. The retort is evacuated to remove objectionable air and moistureand the charge is elevated in temperatui-e until a'point is reached at which the flux dissolves and removes the coating of aluminum oxide from the globulesof molten aluminum. The metal compound is reduced, distilled and condensed in a cooler part of the retort. Hydrogen is then admitted to the retort so that conversion of the reduced hydride-forming metal to its hydride may take place. In the case oi calcium oxide, the unoxidized aluminum of the globules reduces it to calcium; which is then converted by the hydrogen to calcium hydride.

m accordance with my presently preferred method, a charge of hydride-forming metal comp und and particles or slobuiesof aluminum is evacuated to remove air and moisture, preferably while the charge is rising in temperature. It is best to break the vacuum by introducing an inert gas, such as heiium or argon, to place the retort under substantial positive pressu'e. The charge is then heated and subjected to sumcient mixing and grinding in a retort to remove or rupture the refractory coating of, aluminum oxide to such an extent as to bring the unoxidized molten aluminun into reactive contact with the hydride-forming metal compound and thereby cause the desired reducing action to take place. In other words, the mixing and grinding take place during the reaction. To this end, the charge is heated to a temperature above the melting point but below the boilins point of the aluminum. The refractory coatins of aluminum oxide on the resulting globules o! molten aluminum is removed, at least in part, or ruptured and unoxidized molten aluminum is then brought into reactive contact with the particles of hydride-forming metal compound to eflect their reduction. The reduced metal is distilled and condensed in' a cooler part of the retort. Hydrogen gas is then passed into the retort to efi'ect conversion of the reduced hydride-forming metal, calcium !or example, to its hydride.

The invention will be better understood by referring to the following description, taken in conjunction with the accompanying drawing, in which:

' Fig. 1 is a diagrammatic front elevation, partly ,in section, of an apparatus employable in the practice of the method of the invention;

Fig. 2 is a plan view on a reduced scale; and

Fig. 3 .is a fragmentary side view.

The apparatus shown comprises a pot retort i. suitably suspcnded within a furnaoe li having a heating chamber I! with a conduit il near the bottom and a flue opening M near the top thereof through which to introduce heating gafies and to remove s'pent gases from the chamber.

,The retort is advantageously made of beat-resistant steel. It is provided with a removable cover i! bolted to a flange il extending circumferentially around the open end oi' the retort, a gasket ll being located between the two. The retort is suspended in the chamber by means of a plurality of spaoed supports II extending 4 between the flange and the top of the furnaoe. .A

pipe il with a valve !I fltsvinto the cover !or the introduction of hydrogen gas to the interior or reaction zone !I of the retort. The cover is also provided with a charging conduit 22 to supply hydride-forming metal compound and aluminum to the interior of the retort. As shown, the conduit is iltted with three spaced valves u, 24. and !I to provide an evacuatlng passageway !I and a trap 21 of sumcient size to receive a substantial charge 28 of the materials. A pipe !I with a valve !I connects' the evacuating passageway with a source of vacuum, not shown.

example 15 pounds.

#Pa s A mechanical mixing and grinding device !I fits within the interior of the retort. It is provided with a vertical shai't 32, the upper end of which extends through the cover and is suit-` ably held in position by a bearing II and a cols lar 34 screwed to the shaft. The upper end of the shaft is also equipped with a' pulley ll connectible with a source ofpower, not shown.

The intermediate part of shaft 32 is fltted-with a pair of opposed latera arms :I and 31 to each 1'0 of which a pair of depending suppor 'II and ll, respectively, is pivotally attached. The upper end of each depending support is attached to a sleeve ll which fits loosely on the lateral arms and, therefore, permits a pivoting action. Each sleeve is provided with a slot u fltted with a stud bolt or other retaining means secured to the lateral arms. This arrangement' permits the sleeves to pivot or rotate about the latera arms to the extent allowedby the slots: and lateral movement of the sleeves' on the lateral arms is prevented, thus maintaining'the depending supports in spaced relationship to one another.

A heavy mixins and g'indins block I! is secured to the lower end of each depending' support. The lower or grinding face u is inclined or tapered upwardly toward the direction of travel. as shown in Figs. 1 and 3, so that charge materials are worked thereunder as the blocks move in a circle across the bottom of the retort. The/ lower end of shaft 32 terminates in a flattened portion M extending almost to the bottom of the retort and is adapted to push -adjacent charge materials toward and under the grlnding blocks.

The shaft u, and hence tlateral arms u and 85 31, depending supports !l and ll and blocks u are rotated at a rate adapted to provide the desired mixing and grinding action. The particl'es ot charge materials are ground and frictionally rubbed against one another to suchan extent 40 'that the refractory coating of aluminum, oxide is 'removed or ruptured, and the unoxidized molten aluminum is brought into reactive contact with the hydride-forming metal compound.

A dlscharge conduit ll cor'nects with the bottom of the retort and extends .through the bottom of the furnace. A valve u is provided in the conduit below the fumace bottom for the removal of treated charges from the retort.

A pipe I! connecting a source of inert gas. such n as helium or argon, not shown, connects with the interior of the retort. This pipe, with a valve il, conveniently connects with pipe I I. as

I shown.

In accordance with a practice of the invention, ss

cover Il is appropriately bolted to flange II to assure a sealed joint. Heating gases are' passed through conduit I: into heating chamber ii, so

that the' bottom of the retort is heated. spent heating gases escape through flue opening II. ..o valves II, 24, and II are opened and valves II,

23, and u are closed until the air, moisture and other gaseous products are evacuated from the interier of the retort. This may be accomplished by connecting conduit !I with a vacuum pump. ll

not shown. To hasten the evacuation step, the temperature of the interier of the retort may. for example, be raised to arounddoo' C. Toward the end of the evacuation period. 'valve Il is opened and some inert gas is advantageouly 10 i passed through pipe I! into' the retort. Helium or rgon are useful for this purpose. Enough of the gas introduced to place the interior of the retort under substantial positive pressure, for

oa completion of the evacuation step, valves ll and Il are closed, valve 28 is opened and a loose charge of calcium oxide. for example, and aluminum !i is passed into conduit 22 and dropped into trap 21; after which valve !I is closed and valve !I is opened to evacuate trap Il. valves; '24 and !I are then'closed and valve Il isopened so that the evacuated charge is dropped into the retort. The depth of the charge is prefer- I'I so that charge materials and particularly molten aluminum does not enter sleeves ll.

Additional heating gases are passed into heating chamber |2 to raise the temperature of 700-800 C. gives satisfactory results, and has the advantage of not being as injurious to the retort as would a temperature close to the boiling point of the aluminum. It is necessary. however, to have a temperature at which the globules of aluminum are maintained in a molten condi tion. While the temperature may bechecked in various ways, it is practical to employ a hollow shaft 32, in which is placed a suitable thermocouple. If the temperature tends to rise above that desired, cooling air may be forced through I conduit !3 into chamber I! in amounts adapted to dissipate the extra heat. The reduced calcium is dlstilled and condensed more or less -as a circumferential'body II in a cooler part of the retort. Hydrogen gas' is then introduced into the retort to convert the -condensed calcium to the desired calcium hydride; some or all oi' the inert' gas may be evacuated from the retort to make place for the hydrogen. Dueto the exothermic character of the hydriding reaction, it is preferable to add the hydogen slowly while the retort is filled with the inert gas, for example as described in my copending application serial' No.

544,047, filed July 8,- 1944, in order to prevent v .obiectionable fusion of the reduced metal as well as dissociation of the newly-!o med metal The resulting calcium hydride is' permitted to cool in a non-oxidizing atmosphere. such as the hydrogen, or inert gas, until -it can be brought safely into contact with the atmosphere. Lid

ll, is then removed and the calcium hydride is scraped from the retort wall and suitably recovered.

Among the hydride-forming metal compounds that may be treated in accordance with the invention are the oxdes of the alkeline-earth metals, particularly calcium'oxide. strontium oxide and barium oxide. These' compounds .are reduced bythe aluminum and the reduced metal is converted by the hydrogen to its hydride calcium hydride, strontium dride'.

hydrlde and barium hyn will be clear to those skilled' inthisart that the example given is by way of' illustravtion and that the practice of the invention len ls u itself readily to other useiul modiflcations.

ably kept below the level of lateral arms II and the charge within the retort to, for example. 4

7 I claim: 1. In the method of producing metal hydrides. the improvement which comprises heating a charge of a ioose mixture o! a hydride-forming' metal compound and aluminum in a reactionzone to a temperature above the melting point but below the boiling point of the aluminum, the boiling point of the metal of the hydride-forming metal compound being lower than that of the aluminum. removing the refractory coating of aluminum oxide at least in part from globules oi! molten aluminum present in the charge, bringing unoxidized molten aluminum of the globules into reactive contact with the hydride-torming metal compound. distiiing the resulting reduced metal. condensing the distiiled metal in a cooler part of the reaction zone. and then admitting I retractory coating of aluminum oxide on the' gobules of molten aluminum is removed y heating the charge in the presence of a flux that dissoives the aluminum oxide coating:

4. Method according to claim 1,' in which the retractory coating oi' aluminum oxide on the giobules of molten aluminum is removed by mixing andgrinding the charge during the resulting reaction in amount suflicient to break up the aluminum oxide coating so that unoxidized molten aluminum within the globules is brought into reactive contact with the hydride-forming metal compound.

5. Method according to claim 1, in which the reaction zone and charge are initially heated and evacuated to remove air and moisture, and inert gas is admitted into the reaction zone in amount suflicient to place it under substantial positive preseure.

6. In the method of producing metal hydrides, the improvement which comprises heating a charge of an alkaline-earth metal oxide and `aluminum in a reaction none to a temperature above the meiting point but below the boiling point o! the aluminum. removing the refractory coating of aluminum oxide at least in part from lobuies o! molten aluminum present in the charge. bringing unoxidized molten aluminum of the globuies into reactive contact with the alkallne-earth metal compound, distiliing the resulting reduced maune-earth metal. eondensing the distilled me in a eooer part ot the reaction zone. and th dmittlng hydrogen gas to the reaction sone to convert the condensed metal to its alkaline-earth metal hydride.

'7. Method accordinz to claim 6. in which the refractory coating ot aluminum oxide on the globule of molten aluminum is removed by placing the heated charge under vacuum sufllcient in amount to expand molten aluminum within the reiractory coating so that unoxidized molten aluminum within the globules is brought into reactive contact with the alkaline-earth metal compound.

s. Method according to claim 6. in which 'the reiractory coating o! aluminum t oxide on the g obcium.

ules oi molten aluminum is removed by heating the charge in the presence of a iiux that dissolves the aluminum oxide coating.

`i). Method according to claim 6, in-which the refractor'y coating oi' aluminum -oxide on the globules of molten aluminum 'is removed by mixing and grinding the charge during the resulting reaction in amount sumcient to break up the aluminum oxide coating so that unoxidised molten aluminum within the globules is brought into reactive contact with the aikaline-earth metal compound.

10. Method according to claim 6, in which the reaction zone and charge are initially heated and evacuated to remove air and moisture. and inert gas is admitted into the reaction sone in amount sumcient to place it under substantia positive pressure. e

11. In the method of producing metal hydrides, the improvement which comprises heating a charge oi' a ioose mixture of an alkaline-earth metal oxide and aluminum in a reaction zone to a temperature above the melting point but below the boiling point ot the aluminum, removing the refractory coating ot aluminum oxide at least in part from giobules ot molten aluminum present inthe charge, bringing unoxidized molten aluminum of the globules into mactive contact with the alkaline-earth metal oide, distilling the resultins reduced alkaline-earth metal, condensing the distiied metal in a cooler part ot the reaction zone', and then admitting hydrogen gas to the reaction zone to convert the condensed metal to its alkaline-earth metal hydride.

12. Method'according to claim 11, in which the retractory coating of\ aluminum oxide on the gobules of molten aluminum is removed by plac- 'ing the heated .cbarge under vacuum sumcientin amount t'o expand\ molten aluminum within the reiractory coating 'so that unoxidised molten aluminum within the globules ia brought into reactive contact with the alkaiine-earth metal compound.

the refractory coating of aluminum oxide on the globules of molten aluminum is removed by heating the charge in the presence of a i'iux that dissolves the aluminum oxide coating.

`14. Method according to claim -11, in which the refractory coating oi' aluminum oxide on theglobues of molten aluminum is removed by mixing and grinding the charge during the resulting reaction in amount sumcient to break up the aluminum oxide coating so that unoxidied moltenaluminum within the globules is brought into reactive contact 'with .the alkaline-earth metal oxide. v

15. Method according to claim 11. in which the reaction zone and charge are initially heated and evacuated to remove air and moiture, and inert gas is admitting into the reaction sone in amount sumcient to place it under substntial positive pressure.

16. In the method of producing metal hydride. the improvement which comprises heating a charge of a ioose mixture oi salcium oxide and aluminum in a. reaction sone to a temperature above the 'melting point but below the boiiing point oi the aluminum. removing the refractor! c'oating oi' aluminum oxide at least in part !rom the globules o! molten aluminum present in the charge; bringing unoxidiaed molten aluminum o! the globules' into reactive contact with the caicium odde. distiling the resulting reduced caicondensing the distilled ealcium in a oooler QAOLSQS part of the reaction zone, and then admitting hy-- drogen gas to the reaction zone to convert the condensed calcium to calcium hydride.

17. Method according to claim 16, in which the refractory coating of aluminum oxide on the globules of molten aluminum is removed by placing the heated charge under vacuum suflicient in amount to expand molten aluminum within the retractory coating so that unoxidized molten aluminum within the globules is brought into reactive contact with the calcium oxide.

18. Method according to claim 16, in which the refractory coating of aluminum oxide on the globules of molten aluminum is removed by heating the charge in the presence of a, fiux that dissolves the aluminum oxide coating.

19. Method according to claim 16. in which the refractory costine of aluminum oxide on the globules of molten eluminum ia removed by mixng and grinding the charge during the resulting reaction in amount'sumcient to break up the auminum oxide coatingso that unoxidized moiten aluminum within the globules is brought into reactive contact with the calcium oxide.

20. Method according to claim 16, in which the reaction zone and charge are initialy heated and evacuated to remove air and moisturc, and nert gas is admitted into the reaction zone in amount sumcient to place it under substantial positive pressure.

PE'I'ER P. ALEXANDER. 

